Methylene-o,o{40 -bis(ethylacethydroximate)

ABSTRACT

A method for synthesizing the novel compound, methylene-O,O&#39;&#39;bis(ethylacethydroximate) by effecting a reflux reaction between (1) a metal salt of ethyl acethydroximate and (2) a disubstituted halo-methane.

0 United States Patent 1 (111 3,709,920 McDowell et al. [451 Jan. 9,1973 541 METHYLENE-0,0'- [56] References Cited BIS ETHYLACETHYDROXIMATEUNITED STATES PATENTS [75] Inventors: Curtis S. McDowell; Mlchael W.

Barnes both f Edwards i Force 2,560,227 7/1951 Kleinschmidt ..260/566 ABase, Calif. Primary Examiner-Leland A. Sebastian [73] ASSgnee: TheUnited sht's America Attorney-Harry A. Herbert, Jr. and William J. 0-

represented by the Secretary of the Brien Air Force 22 Filed: Dec. 3,1969 ABSTRACT 21 A l 32 75 A method for synthesizing the novel compound,

methylene-0,0'-bis(ethylacethydroximate) by effecting a reflux reactionbetween (1)) a metal salt of ethyl [52] US. Cl. ..260/453 R, 149/109acethydroximate and (2) a disubstimted halo [51] Int. Cl. ..C07c 85/04,C07c 87/00 methane [58] Field of Search .260/566 A, 566 AB, 453 R 4Claims, No Drawings BACKGROUND OF THE INVENTION This invention relatesto a new compound and to a method for its preparation. In a moreparticular manner, this invention concerns itself with the synthesis ofmethylene-0,0'-bis(ethylacethydroximate) and to a process for effectingthat synthesis.

I-Ieretofore, considerable difficulty was encountered by thoseattempting to synthesize methylene- 0,0'bis(ethylacethydroximate).

However, in attempting to overcome these difficulties, it was found thatthe new compound methylene- 0,0'-bis(ethylacethydroximate) could besynthesized by effecting a reflux reaction between (1) anethylacethydroximate metal salt and (2) a disubstituted halo-methane.The reactants (1) and (2) are dissolved in a suitable solvent andrefluxed at temperatures of from 25 to 100C over a period of time fromabout one-half to 72 hours.

The new methylene-0,0'-bis(ethylacethydroximate) compound of thisinvention finds utility as an inter mediate or precursor for thesynthesis of methylenedioxyamine and its salts by an acid hydrolysisreaction. Methylenedioxyamine and its salts such as methylenedioxyaminediperchlorate are useful as oxidizers for liquid and solid rocket fuels.

SUMMARY OF THE INVENTION In the present invention, methylene-0,0- bis(ethylacethydroximate) can be synthesized by a reflux reaction between ametal salt of ethyl acethydroximate and a dihalomethane. The reactiontakes place at temperatures ranging from about 25 to 100C over a periodof time of from about one-half to 72 hours.

Accordingly the primary object of this invention is to provide a newcompound and a method for its preparation.

Another object of this invention is to provide a method for synthesizingmethylene-0,0- bis(ethylacethydroximate).

Still another object of this invention is to synthesize the new compoundmethylene-0,0- bis(ethylacethydroximate).

The above and still further objects and advantages of the presentinvention will become apparent upon consideration of the followingdetailed description thereof.

DESCRIPTION OF THE PREFERRED EMBODIMENT In accordance with thisinvention, it has been found that the above noted objects can beaccomplished by effecting a reflux reaction between (1) and ethylacethydroximate basic metal salt such as sodium and potassium ethylacethydroximate and (2) a disubstituted halo-methane such as methylenebromide, methylene iodide and methylene chloride. The reactants aredissolved in a suitable solvent such as acetonitrile, ethanol,dimethylacetamide and dimethylformamide and refluxed over a one-halfhour to 72 hour period at temperatures ranging from 25 to 100C.

The reflux reaction which is believed to take place during thesynthesizing of the novel compound 2methylene-0,0'-bis(ethylacethydroximate) is illustrated by thefollowing:

(I) Acetonitrllo.

Wherein X represents a member selected from the group consisting of Cl,Br and I.

The product of the above described reflux reaction is recovered by thefollowing procedure. The reaction mixture may be filtered to removeprecipitated salts and then distilled or, it may be distilled directlyunder reduced pressure at temperatures of less than 90C to remove thesolvent. The resulting concentrated oil is taken up in ether, methylenechloride or some other solvent in which the salts are insoluble. It isthen washed with water to remove salts and acetamide. The acetamide is aby-product sometimes obtained as a result of decomposition of thebis(ethylacethydroximate). A dilute sodium hydroxide wash for removal ofunreacted ethylacethydroximate may be included but is not necessary.After drying and removal of solvent at reduced pressure, theconcentrated product, ethylacethydroximate mixture, is then distilled atreduced pressure to give unreacted ethylacethydroximate having a boilingpoint of 42C at 4mm and the heretofore unknown methylene-0,0'-bis(ethylacethydroximate) having a boiling point of 6467C at 0.5mm. or aboiling point of 8892 at 4mm. Yields of greater than 85 percent havebeen obtained.

In order to further illustrate to those skilled in the art the best modeof operation for the present invention, there is presented the followingdetailed example. This example, however is presented for purposes ofillustration only and is not to be considered as limiting the scope ofthe invention in any way.

EXAMPLE To 750 ml of dry acetonitrile was added 15.5g of powdered 98percent sodium hydroxide (0.380 mole) and 40 g (0.388 mole) ofethylacethydroximate. The mixture was brought to reflux while stirringand 57.1 g (0.213 mole) of methylene iodide was added dropwise. Themixture was refluxed gently with stirring for 42 hours and then wasstripped of acetonitrile on a rotary evaporator at reduced pressure andat approximately C. The remaining oil was taken up in methylene chloride(approximately twice the volume of the crude oil) and filtered to removethe byproduct sodium iodide. The methylene chloride was stripped atapproximately 40C under reduced pressure to give 51.2 g of a light brownoil. Distillation of this oil at 64-67C and 0.5-0.8 mm gave 39.1 g (92percent) of a colorless liquid comprising an isomeric mixture of pure(IR) methylene-0,0-bis(ethylacethydroximate) A232 6.ll(s), l|.35(s);mmr(CDCl )'y 8.77 and 8.70 two overlapping triplets, (6 CH ethylprotons), 8.09 and 8.05 two singlets, (6 CH acetoprotons), 5.97 and 5.89two overlapping quartets (4CH ethyl protons), 4.72 and 4.69 two singlets(ZOCI-I, protons).]

Analysis calculated for C H N O C, 49.53; H, 8.31; N, 12.83; Analysisfound to be: C, 49.0; H, 8.3; N, l 2.8.

What is claimed is:

l. The compound, bis(ethylacethydroximate).

2. A method for synthesizing methylene-0,0- bis( ethylacethydroximate)which comprise the steps of (l) heating at reflux temperature a solventmixture of methylene-0,0-

two reactants comprising (a) an ethylacethydroximate metal salt and (b)a disubstituted halo-methane, (2) continuing to heat said mixture for aperiod of time suf-

2. A method for synthesizing methylene-O,O''-bis(ethylacethydroximate)which comprise the steps of (1) heating at reflux temperature a solventmixture of two reactants comprising (a) an ethylacethydroximate metalsalt and (b) a disubstituted halo-methane, (2) continuing to heat saidmixture for a period of time sufficient to effect a reaction betweensaid two reactants, and (3) separating the reaction product resultingfrom said reaction.
 3. A method in accordance with claim 2 wherein themetal component of the first reactant is selected from the groupconsisting of sodium and potassium.
 4. A method in accordance with claim2 wherein the halogen component of said second reactant is selected fromthe group consisting of bromine, iodine and chlorine.